DE69402219T2 - Dir coupler with hydrolyzable inhibitors for use in high pH films - Google Patents

Description

Background of the invention

This invention relates to a photographic light-sensitive material, such as a color reversal material, intended for development in a high pH developing solution. In particular, the photographic light-sensitive material contains a novel development inhibitor releasing (DIR) compound capable of releasing a development inhibitor or a precursor thereof upon reaction with the oxidation product of a developing agent. The development inhibitor is such that it is decomposed after diffusion into the high pH developing solution. The invention can be used in the graphic arts sector of photography, as well as in the field of color reversal photography.

Hydrolyzable inhibitor-type DIR couplers have proven useful in color negative processes because the released inhibitor can diffuse within the film to perform its development inhibiting function. However, if the inhibitor enters the color developer solution, the inhibitor hydrolyzes to a compound that has little or no development inhibiting properties, such that the hydrolysis product has no effect on the development of subsequent films developed in the same developer solution. If the decomposition half-life of the inhibitor is too short, the inhibitor in the film can decompose when it comes into contact with the developer solution to such an extent that it does not perform the desired development inhibition. Accordingly, if the half-life of the decomposition is too long, it may happen that the inhibitor does not decompose in the developer in a timely manner and that it has an adverse effect on the development of subsequent films developed in the same developer solution.

U.S. Patent 4,477,563 describes development inhibitor molecules that are converted into an inactive species (with respect to development inhibition) soon after contact with the developing solution.

U.S. Patent 4,782,012 describes preferred hydrolyzable mercaptotetrazole inhibitors; however, these inhibitors are ineffective in films developed at high pH values. U.S. Patent 4,782,012 discloses that the logarithm of the partition coefficient (Log P) is a good measure of the strength of the inhibitor, its mobility, and consequently its ability to produce interimage effects. The patent further discloses that the calculated Log P value (c Log P) is used to determine optimal solubility values for mercaptotetrazole inhibitors. Log P is the logarithm of the partition coefficient of a species between a standard organic phase, usually octanol, and an aqueous phase, usually water. Color photographic elements are multiphase systems and a photographic inhibitor released in such a system can partition between these different phases. Log P serves as a measure of this distribution and can be correlated to desirable inhibitor properties such as inhibitor strength and interimage effects.

Inhibitor residues with values of c Log P below 0.40 have been found to be too weak as inhibitors in the present invention and do not have suitable intermediary properties. The c Log P values used in this specification, unless otherwise stated, were calculated using the additive fragment technique of C. Hansch and A. Leo, described in "Substituent Constants for Correlation Analysis in Chemistry and Biology", Wiley Publishers, New York, 1979, using the computer program "MedChem", version 3.54, Medicinal Chemistry Project, Pomona College, Claremont, CA (1989).

US-A-4,798,784, US-A-4,937,179, US-A-5,004,677, EP-A-219,713 and EP-A-488,310 describe DIR couplers with hydrolyzable inhibitors and teach a preferred half-life period of the inhibitor at pH 10.0 of no more than 4 hours.

Published Japanese Application 2 251 950 describes a silver halide-based color photographic material containing carboxyester-substituted mercaptooxadiazole and mercaptothiadiazole fragments.

European application 440 466 describes a silver halide photographic material containing couplers releasing hydrolysable mercaptooxadiazole development restrainers.

It follows that the prior art only describes a preferred half-life period of the inhibitor at a pH of 10.0 of no more than 4 hours. Compounds described in the prior art are not intended for films that are developed using processes with high pH values (pH > 11.4).

Consequently, there is a strong need for photographic materials that are processed in high pH developers to produce enhanced interimage effects, or that provide acutance or sharpness benefits by application of image-modifying chemistry without adverse contamination of the high pH developer solution caused by infusion of development inhibitors released from DIR compounds during the development process.

The present invention meets this need and overcomes the problems caused by the use of DIR compounds or couplers in films developed in high pH developers, such as color reversal silver halide light-sensitive photographic materials, suitable for development in a colour reversal process by providing an improved film element comprising:

a silver halide photographic light-sensitive material for development in a developing solution at a pH of at least 11.4, the material comprising a support having a silver halide emulsion layer containing a compound capable of releasing a development inhibitor having a decay half-life in the range of over 4 to 225 hours, preferably 6 to 120 hours, at a pH of 10, the inhibitor having substantially no photographic inhibitory properties after decomposition, and the compound having the formula:

CAR-(TIME)n-INH-L-Y (I)

wherein:

CAR is a carrier residue which releases the moiety -(TIME)n-INH-L-Y by reaction with oxidized developer;

TIME is a time control group;

INH-L-Y is a development inhibitor moiety, wherein INH is selected from the group consisting of substituted or unsubstituted oxazole, thiazole, diazole, oxathiazole, triazole, thiatriazole, tetrazole, benzimidazole, indazole, isoindazole, mercaptothiazole, mercaptotriazole, mercaptothiadiazole, mercaptotetrazole, selenotetrazol, mercaptooxadiazole, selenobenzothiazole, mercaptobenzoxazole, selenobenzoxazole, mercaptobenzimidazole, selenobenzimidazole, benzodiazole or benzisodiazole, such that an inhibitor moiety having the moiety H-INH-L-Y has a calculated log P value of greater than 0.4;

n is 0, 1 or 2;

L is a linking group with a chemical bond that is broken in a photographic processing solution, which includes the following groups:

-CO₂-, -NReCO₂-, -SO₂O-, -OCH₂CH₂SO₂-, -OC(=O)O- or -NReC(=O)C(=O)-, wherein Re is hydrogen, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group; and wherein L may be introduced into INH-L-Y such that either end of L (as indicated above) may be bonded to INH;

Y represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. When Y represents an alkyl group, the alkyl group may be substituted or unsubstituted or an unsubstituted or straight or branched chain or a cyclic group. Y may contain 1 to 5 alkylthio groups. The total number of carbon atoms in Y is preferably 1 to 25. The alkyl group may in turn be substituted by the same groups given for R below. When the group Y consists of an aryl group, the aryl group may be substituted by the same groups given for R. When Y represents a heterocyclic group, the heterocyclic group is a 5- or 6-membered monocyclic or condensed ring containing a nitrogen atom, an oxygen atom or a sulfur atom as a heteroatom. Examples of these are a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group, an oxazolyl group, an imidazolyl group, a thiazolyl group, a triazolyl group, a benzotriazolyl group, an imido group and an oxazine group. The heterocyclic group may be substituted by the same groups given for R. Other INH-L-Y residues may include benzotriazoles or mercaptobenzothiazoles.

Linking groups or timing groups, when present, are groups such as ester and carbamate groups that are subject to base-catalyzed cleavage, including anchimerically assisted hydrolysis or intramolecular nucleophilic displacement. Suitable linking groups, also known as timing groups, are described in U.S. Patents 5,151,343, 4,857,447, 5,021,322, 5,026,628, and 5,051,345. Preferred linking groups are o- and p-hydroxymethylene radicals as described in the aforementioned U.S. Patent 5,151,343 and in couplers T16 and T1 of the present application, respectively, and o-hydroxyphenyl substituted carbamate groups.

CAR groups include couplers that react with oxidized color developer to form dyes while simultaneously releasing development inhibitors or inhibitor precursors. Suitable carrier groups include hydroquinones, catechins, aminophenols, aminonaphthols, sulfonamidophenols, pyrogallols, sulfonamidonaphthols, and hydrazides that are subject to cross-oxidation by oxidized color developer. DIR compounds with carriers of this type are described in U.S. Patent 4,791,049. Preferred CAR groups are couplers that provide unballasted dyes that are removed from the photographic element during the development process, such as those described in the aforementioned U.S. Patent 5,151,343. Furthermore, preferred carrier groups are couplers which provide ballasted dyes that match the spectral absorption characteristics of the image dye, as well as couplers which provide colorless products.

According to one embodiment of the invention, a three-color reversing element has the following schematic structure:

(13) second protective layer containing matting agent (matte)

(12) first protective layer containing UV-absorbing dyes

(11) highly sensitive, blue-sensitive layer containing a blue-sensitive emulsion and a yellow coupler

(10) less sensitive, blue-sensitive layer containing a blue-sensitive emulsion and a yellow coupler

(9) Yellow filter layer

(8) Intermediate layer

(7) highly sensitive, green-sensitive layer containing a green-sensitive emulsion and a magenta coupler

(6) less sensitive, green-sensitive layer containing a green-sensitive emulsion and a magenta coupler

(5) Intermediate layer

(4) highly sensitive, red-sensitive layer containing a red-sensitive emulsion and a cyan coupler

(3) less sensitive, red-sensitive layer containing a red-sensitive emulsion and a cyan coupler

(2) Intermediate layer

(1) Antihalation layer Carrier with an adhesion-improving layer.

In the following discussion of suitable materials for use in the emulsions and elements of this invention, reference is made to Research Disclosure, December 1989, No. 308119, published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, Hampshire, P010 7DQ, UK. This reference is hereinafter referred to as Research Disclosure.

Couplers which form cyan dyes upon reaction with oxidized color developing agents are described in such representative patents and publications as U.S. Patents 2,772,162; 2,895,826; 3,002,836; 3,034,892; 2,747,293; 2,423,730; 2,367,531; 3,041,236 and 4,333,999; and in Research Disclosure, Section VII D. Preferably, such couplers are phenols and naphthols.

Couplers which form magenta dyes upon reaction with oxidized color developing agents are described in such representative patents and publications as: U.S. Patents 2,600,788; 2,369,489; 2,343,703; 2,311,082; 3,152,896; 3,519,429; 3,062,653 and 2,908,573 and Research Disclosure Section VII D. Preferably, such couplers are pyrazolones and pyrazolotriazoles.

Couplers which form yellow dyes upon reaction with oxidized color developing agents are described in such representative patents and publications as: U.S. Patents 2,875,057; 2,407,210; 3,265,506; 2,298,443; 3,048,194; and 3,447,928 and Research Disclosure, Section VII D. Preferably, such couplers are acylacetamides such as benzoylacetanilides and pivaloylacetanilides.

Couplers which form colorless products upon reaction with oxidized color developing agents are described in such representative patents as: UK Patent 861,138; U.S. Patents 3,632,345; 3,928,041; 3,958,993 and 3,961,959. Preferably, such couplers are cyclic carbonyl group-containing compounds which react with oxidized color developing agents but do not form dyes.

The image dye-forming couplers can be incorporated into photographic elements and/or used in photographic processing solutions, such as developer solutions, so that when an exposed photographic element can form a reactive combination with oxidized color developing agent. Coupler compounds incorporated into photographic processing solutions should be of such molecular size and configuration that they diffuse through photographic layers with the processing solution. When incorporated into a photographic element, the general rule is that the image dye-forming couplers should be non-diffusible; that is, they should be of such molecular size and configuration that they do not migrate to any significant extent from the layer in which they are coated.

Photographic elements of this invention can be processed by conventional techniques in which color forming couplers and color developing agents are incorporated into separate processing solutions or compositions or into the element, such as described in Research Disclosure, Section XIX.

High pH processes as described in this invention include the E-6 process described in the Manual For Processing Kodak Ektachrome Films Using E-7, (1980) Eastman Kodak Company, Rochester, N.Y., or a substantially equivalent process developed by a company other than Eastman Kodak Company. These processes are referred to as "current" color reversal processes or "standard" processes. In these processes, the pH of the color developer solution is from about 11.6 to about 12.1. The color developer solution is used in this process for about 5.5 to 7.0 minutes at a temperature of 36.6 to 39.4°C. The processing of reversal elements typically involves first treating the element with a black-and-white developer to develop exposed silver halide grains, then fogging unexposed grains, then treating the element with a color developer.

Preferred INH-LY groups according to the invention can be selected are made up of groups with the following structures:

wherein R' is selected from an alkyl group, an aryl group or a 5- or 6-membered heterocyclic ring, an alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, sulfamoyl group, sulfonamido group, sulfoxyl group, carbamoyl group, alkylsulfo group, arylsulfo group, aryloxycarbonylamino group, alkoxycarbonylamino group, acylamino group, ureido group, arylthio group, alkylthio group. If R' is an alkyl group, the alkyl group can be substituted or unsubstituted or straight-chain or branched-chain or cyclic. The group R' can contain 1 to 5 alkylthio groups. The total number of carbon atoms in R' is 1 to 25. The alkyl group can in turn be substituted by R, where R can be selected from the groups given for R' above, but R can also be selected from hydrogen, halogen (including fluorine, chlorine, bromine and iodine), a hydroxy group or a cyano group. If the group R' is an aryl group, the aryl group can be substituted by the same groups given for R. If R' is a heterocyclic group, the heterocyclic group is a 5- or 6-membered monocyclic or condensed ring containing as a heteroatom a nitrogen atom, oxygen atom or a sulfur atom. Examples include a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group, an oxazolyl group, an imidazolyl group, a thiazolyl group, a triazolyl group, a benzotriazolyl group, an imido group and an oxazine group. The heterocyclic group may be substituted by the same groups listed for R. If two or more R groups are present on a molecule, R may be the same or different; n may be 0, 1 or 2 and m may be 0, 1, 2 or 3.

Further preferred INH-LY groups are selected from, but are not limited to, the following examples:

Preferably, CAR is a coupler residue and furthermore the coupler residue can comprise ballast.

In the element according to the invention, the group -(TIME)n-INH-L-Y is attached to a coupling position of the coupler moiety. Preferably, CAR is unballasted and at least one TIME moiety attached to CAR is ballasted and CAR is preferably a coupler moiety.

Furthermore, CAR is preferably a residue that undergoes cross-oxidation with oxidized color developer and can be selected from the class consisting of hydrazides and hydroquinones.

Compound (I) may be present in the element in an amount of 0.005 to 0.3 g/m² (0.5 to 30 mg/ft²) and is typically present in the element in an amount of 0.01 to 0.1 g/m² (about 1 to 10 mg/ft²).

CAR can be, for example, a coupler moiety, denoted by COUP, which forms a dye as part of a coupling reaction, or an organic moiety which does not form a dye. The purpose of CAR is to provide, as a function of color development, a fragment INH-L-Y or INH-L-Y attached to a linking group or timing group, or to a combination of linking and timing groups, denoted by -(TIME)n-. As long as CAR performs this function in an effective manner, the group has served its purpose in the context of this invention.

If COUP is a yellow coupler residue, coupler residues with the general formulae II-IV are preferred. If COUP is a magenta coupler residue, it is preferred that COUP has the formula (V) or (VIII). If COUP is a cyan coupler residue, it is preferred that COUP has the formula represented by the general formulae (VI) and (VII).

Furthermore, CAR can be a redox residue, which is a group capable of undergoing cross-oxidation with an oxidation product of a developing agent. Such carriers can consist of hydroquinones, pyrocatechols, pyrogallols, aminonaphthols, aminophenols, naphthohydroquinones, sulfonamidophenols and hydrazides. Compounds with carriers of this type are described in US Patent 4,791,049. Preferred CAR fragments of this type are represented by the general formulas (X) and (XI). Compounds in the context of formulae (IX) and (XII) are compounds which react with oxidized developer to form a colorless product or a dye which is decolorized by further reaction. As long as the film comprises an image-modifying compound of the type described herein in an image-forming layer, the film has the construction described for this invention. It should be noted, however, that the film may comprise two or more of the described image-modifying compounds in an image-forming silver halide emulsion layer or that two or more such layers may contain one or more of the described image-modifying compounds.

In general, the compound (I) is represented, for example, by the following structures:

In the case of the above compounds, X = -(TIME)n- INH-L-Y and R₁ represents an aliphatic group, an aromatic group, an alkoxy group or a heterocyclic ring, and R₂ and R₃ each represent a hydrogen atom, an aromatic group, an aliphatic group or a heterocyclic ring. The aliphatic group represented by R₁ preferably contains 1 to 30 carbon atoms and may be substituted or unsubstituted, straight-chain or branched-chain or cyclic. Preferred substituents for an alkyl group include an alkoxy group, an aryloxy group, an amino group, an acylamino group and a halogen atom. These substituents may be substituted per se. Suitable examples of aliphatic groups represented by R₁, R₂ and R₃ are: are the following groups: an isopropyl group, an isobutyl group, a tert-butyl group, an isoamyl group, a tert-amyl group, a 1,1-dimethylbutyl group, a 1,1- dimethylhexyl group, a 1,1-diethylhexyl group, a dodecyl group, a hexadecyl group, an octadecyl group, a cyclohexyl group, a 2-methoxyisopropyl group, a 2-phenoxyisopropyl group, a 2-p-tert-butylphenoxyisopropyl group, an α-aminoisopropyl group, an α-(diethylamino)isopropyl group, an α-(succinimido)isopropyl group, an α-(phthalimido)isopropyl group, and an α-(benzenesulfonamido)isopropyl group. When two groups R₁ or R₃ occur, , they can be the same or different.

When R₁, R₂ or R₃ represents an aromatic group (particularly a phenyl group), the aromatic group may be substituted or unsubstituted. That is, the phenyl group may be used per se or it may be substituted by a group having 32 or less carbon atoms, for example, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an alkoxycarbonylamino group, an aliphatic amido group, an alkylsulfamoyl group, an alkylsulfonamido group, an acylureido group and an alkyl-substituted succinimido group. This alkyl group may be an aromatic group, for example a phenylene group in the chain. The phenyl group can also be substituted, for example by an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamido group or an arylureido group. In these substituents, the aryl group part can be further substituted by at least one alkyl group containing 1 to 22 carbon atoms in total.

The phenyl group represented by R₁, R₂ or R₃ may be substituted by an amino group, which may be further substituted by a short-chain alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, a sulfo group, a nitro group, a cyano group, a thiocyano group or a halogen atom.

In addition, R₁, R₂ or R₃ may further represent a substituent resulting from the condensation of a phenyl group with another ring, for example, a naphthyl group, a quinolyl group, an isoquinolyl group, a furanyl group, a coumaranyl group and a tetrahydronaphthyl group. These substituents may be further substituted per se.

When R1 represents an alkoxy group, the alkyl part of the alkoxy group contains 1 to 40 carbon atoms and preferably 1 to 22 carbon atoms and is a straight-chain or branched-chain alkyl group, a straight-chain or branched-chain alkenyl group, a cyclic alkyl group or a cyclic alkenyl group. These groups can be substituted, for example, by a halogen atom, an aryl group or an alkoxy group.

When R₁, R₂ or R₃ is a heterocyclic ring, the heterocyclic ring is bonded through one of the carbon atoms in the ring to the carbon atom of the carbonyl group of the acyl group in the α-acylacetamide or to the nitrogen atom of the amido group in the α-acylacetamide. Examples of such heterocyclic rings are thiophene, furan, pyran, pyrrole, pyrazole, pyridine, Piperidine, pyrimidine, pyridazine, indolizine, imidazole, thiazole, oxazole, triazine, thiazine and oxazine. These heterocyclic rings can have a substituent on the ring.

In the structural formula (V), R₄ contains 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms and is a straight-chain or branched-chain alkyl group (for example, methyl, isopropyl, tert-butyl, hexyl and dodecyl), an alkenyl group (for example, an allyl group), a cyclic alkyl group (for example, a cyclopentyl group, a cyclohexyl group and a norbornyl group), an aralkyl group (for example, a benzyl group and a β-phenylethyl group), or a cyclic alkenyl group (for example, a cyclopentenyl group and a cyclohexenyl group). These groups may be substituted, for example, by a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, an alkylthiocarbonyl group, an arylthiocarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, a urethane group, a thiourethane group, a sulfonamido group, a heterocyclic group, an arylsulfonyl group, an alkylsulfonyl group, an arylthio group, an alkylthio group, an alkylamino group, a dialkylamino group, an anilino group, an N-arylanilino group, an N-alkylanilino group, an N-acylanilino group, a hydroxyl group and a mercapto group.

R₄ may further represent an aryl group, for example a phenyl group and an α- or β-naphthyl group. This aryl group contains at least one substituent. These substituents include an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, a urethane group, a sulfonamido group, a heterocyclic group, an arylsulfonyl group, an alkylsulfonyl group, an arylthio group, an alkylthio group, an alkylamino group, a dialkylamino group, an anilino group, an N-alkylanilino group, an N-arylanilino group, an N-acylanilino group, a hydroxyl group and a mercapto group.

More preferably, R4 represents a phenyl group which is substituted, for example, by an alkyl group, an alkoxy group or a halogen atom in at least one of the ortho positions.

R4 may further represent a heterocyclic ring (for example, a 5- or 6-membered heterocyclic or condensed heterocyclic group having a nitrogen atom, an oxygen atom or a sulfur atom as a heteroatom, such as a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group, an oxazolyl group, an imidazolyl group and a naphthoxazolyl group), a heterocyclic ring substituted by the groups described for the aryl group described above, an aliphatic or aromatic acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group.

R₅ represents a hydrogen atom, a straight-chain or branched-chain alkyl group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group (which may have substituents as indicated for R₄), an aryl group and a heterocyclic group (which may have substituents as indicated for R₄), an alkoxycarbonyl group (for example, a methoxycarbonyl group, an ethoxycarbonyl group and a stearyloxycarbonyl group), an alkoxycarbonyl group (for example a phenoxycarbonyl group and a naphthoxycarbonyl group), an aralkyloxycarbonyl group (for example a benzyloxycarbonyl group), an alkoxy group (for example a methoxy group, an ethoxy group and a heptadecyloxy group), an aryloxy group (for example a phenoxy group and a tolyloxy group), an alkylthio group (for example an ethylthio group and a dodecylthio group), an arylthio group (for example a phenylthio group and an α-naphthylthio group), a carboxyl group, an acylamino group (for example an acetylamino group and a 3-[(2,4-di-tert.-amylphenoxy)acetamido]benzamido group), a diacylamino group, an N-alkylacylamino group (for example an N-methylpropionamido group), an N-arylacylamino group (for example an N-phenylacetamido group), a ureido group (for example Example a ureido group and an N-arylureido group), a urethane group, a thiourethane group, an arylamino group (for example a phenylamino group, an N-methylanilino group, a diphenylamino group, an N-acetylanilino group and a 2-chloro-5-tetradecanamidoanilino group), a dialkylamino group (for example a dibenzylamino group), an alkylamino group (for example an n-butylamino group, a methylamino group and a cyclohexylamino group), a cycloamino group (for example a piperidino group and a pyrrolidino group), a heterocyclic amino group (for example a 4-piperidylamino group and a 2-benzoxazolylamino group), an alkylcarbonyl group (for example a methylcarbonyl group), an arylcarbonyl group (for example a phenylcarbonyl group), a sulfonamido group (for example an alkylsulfonamido group and an arylsulfonamido group), a carbamoyl group (for example, an ethylcarbamoyl group, a dimethylcarbamoyl group, an N-methylphenylcarbamoyl group and an N-phenylcarbamoyl group), a 4,4'-sulfonyldiphenoxy group, a sulfamoyl group (for example, an N-alkylsulfamoyl group, an N,N-dialkylsulfamoyl group, an N-arylsulfamoyl group, an N-alkyl-N-arylsulfamoyl group and an N,N-diarylsulfamoyl group), a cyano group, a hydroxyl group, a mercapto group, a halogen atom or a sulfo group.

R₆, R₇ and R₈ each represent groups used in the case of the usual phenol or α-naphthol 4-equivalent type couplers. More specifically, R₆ represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an acylamino group, -O-R₉ or -S-R₉ (wherein R₉ is an aliphatic hydrocarbon group). When two or more R₆ groups are present in the same molecule, they may be different. The aliphatic hydrocarbon groups include those containing one or more substituents. R₆ and R₈ each represent an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. One of R₆ and R₈ may be a hydrogen atom, and the above-described groups for R₇ and R₈ may be substituted. R₇ and R₈ may together form a nitrogen-containing heterocyclic nucleus. In the formulas, q is an integer from 1 to 3 and p is an integer from 1 to 5.

R₁₀ is an acylamido group represented by COR₁, a carbamoyl group represented by CONHR₇R₈, a sulfonamido group represented by SO₂R₁ or SO₂NR₇R₈.

The aliphatic hydrocarbon residue may be saturated or unsaturated, straight-chain, branched-chain or cyclic. Preferred examples are an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, an isobutyl group, a dodecyl group, an octadecyl group, a cyclobutyl group, and a cyclohexyl group), and an alkenyl group (for example, an allyl group and an octenyl group).

The aryl group includes a phenyl group and a naphthyl group, and typical examples of heterocyclic groups are a pyridinyl group, a quinolyl group, a thienyl group, a piperidyl group and an imidazolyl group. Substituents that can be introduced into these aliphatic hydrocarbon, aryl and heterocyclic groups include a halogen atom, a nitro group, a hydroxyl group, a carboxyl group, an amino group, a substituted amino group, a sulfo group, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an arylthio group, an arylazo group, an acylamino group, a carbamoyl group, an ester group, an acyl group, an acyloxy group, a sulfonamido group, a sulfamoyl group, a sulfonyl group and a morpholino group.

In the compounds (II) to (XII), the substituents R₁, R₂, R₃, R₄, R₅, R₆, R₃, R₆, R₇ and R₈ may combine with each other to form symmetrical or asymmetrical composite couplers, or any of the substituents may become a divalent group to form symmetrical or asymmetrical composite couplers.

In the case of the compounds of formula VIII: S₁₀, S₁₁ and S₁₂ each represent a methine group, a substituted methine group, =N-, or -NH-; one of the S₁₀-S₁₁ bond and the S₁₁-S₁₂ bond is a double bond and the other bond is a single bond; when S₁₁-S₁₂ is a carbon-carbon double bond, the double bond may be part of an aromatic ring; the compound of general formula VIII includes the case of forming a dimer or a higher polymer at R₄; further, when S₁₀, S₁₁ or S₁₂ represents a substituted methine group, the compound includes the case where it forms a dimer or higher polymer with the substituted methine group. Polymer formation can also take place through the linking group -(TIME)n- in all image-modifying compounds used in this invention.

If R₁ to R₁₀ of structural formulae II to VIII represent a ballast such that the dye formed upon reaction with oxidized developer remains in the film after development, then the formulae are represented by examples of type II.

Particularly preferred are those couplers which undergo a coupling reaction with an oxidation product of a developing agent, release a development inhibitor, but do not leave a dye in the film which could lead to a reduction in color quality. If R₁ to R₁₀ of the compounds II to VIII do not represent a ballast such that the dye later formed from CAR is not immobilized and is removed from the film during the development process, then the formulas are represented by examples of type I. Also included in examples of this type I are the formulas IX, X, XI and XII in which R₁ to R₈ are constitute a ballast, however, CAR either yields a colourless product or does not form a dye upon reaction with oxidised developer (as in the case of compounds XI and XII) or the dye which is formed is decolourised by subsequent reactions in the process (as in the case of compounds IX and XII).

Also, preferred structures that would produce the same effects as DIR couplers without leaving a dye in the film are those in which CAR is a material capable of undergoing a redox reaction with the oxidized product of a developing agent and subsequently releasing a development inhibitor, as described in U.S. Patent 4,684,604 and represented by compound X where T is a substituted aryl group. T can represent phenyl, naphthyl; and heterocyclic rings (for example pyridyl) and can be substituted by one or more groups such as alkoxy, alkyl, aryl, halogen, and those groups described for R5.

In the case of the compounds of formula (I), -(TIME)n-INH-L-Y represents a group which is not released until after reaction with the oxidized developing agent, either by cross-oxidation or dye formation.

In the compounds of formula (I), -(TIME)n- represents one or more linking or timing groups which is or are linked to CAR through an oxygen atom, a nitrogen atom or a sulfur atom capable of releasing INH-L-Y from -(TIME)n-INH-L-Y at the time of evolution through one or more reaction steps. Suitable examples of these types of groups can be found in U.S. Patents 4,248,962, 4,409,323, 4,146,396, British Patent 2,096,783, and Japanese Patent Applications (Opi) 146828/76 and 56837/82.

Preferred examples of -(TIME)- are those represented by the following examples XIII - XX:

In each of the above compounds, the bond on the left is attached to either CAR or another -(TIME)- residue and the bond on the right is attached to INH.

The group R₁₁ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkoxycarbonyl group, an anilino group, an acylamino group, a ureido group, a cyano group, a nitro group, a sulfonamido group, a sulfamoyl group, a carbamoyl group, an aryl group, a carboxy group, a sulfo group, a hydroxy group or an alkanosulfonyl group. The Alkyl group at R₁₁ contains 1 to 32 carbon atoms. In the general formulas XIII-XX, Z stands for oxygen, nitrogen or sulfur and k is a number from 0 to 2.

R₁₂ represents hydrogen, alkyl, perfluoroalkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, (R₂)₂N-, R₁CONR₇- or a heterocyclic group; (R₁₂)₂ may complete a non-aromatic heterocyclic or a non-aromatic carbocyclic ring and R₁₂ and R₁₁ may complete a non-aromatic heterocyclic or a non-aromatic carbocyclic ring.

In timing groups XIII, XIV, XV and XVII, R11 can complete a carbocyclic or heterocyclic ring or ring system. Completed rings include derivatives of naphthalene and quinoline.

If n=0, -(TIME)- can also represent a single bond such that CAR can be directly bound to INH-L-Y.

In case of n=2, there can be a combination of any two timing groups as mentioned in the case of formula XIII to XX, which still allow the fragmentation and release of INH-LY during color development after CAR has reacted with the oxidized developer. The combination of two timing groups can be used to improve the release of the inhibitor fragment INH-LY, either by the rate of release and/or the diffusivity of -(TIME)n-INH-LY or any subsequent fragments of the moiety. For example, preferred structures are:

Illustrative, but not limiting, image-modifying compounds that can be used in this invention are the following:

To incorporate the compounds of the present invention and couplers used together therewith into a silver halide emulsion layer, known methods including, for example, those described in U.S. Patent No. 2,322,027 may be used. For example, they may be dissolved in a solvent and then dispersed in a hydrophilic colloid. Examples of solvents that can be used for this process include organic solvents with a high boiling point, such as alkyl esters of phthalic acid (for example, dibutyl phthalate and dioctyl phthalate), phosphoric acid esters (for example, diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and dioctyl butyl phosphate), citric acid esters (for example, tributyl acetyl citrate), benzoic acid esters (for example, octyl benzoate), alkylamides (for example, diethyl laurylamide), esters of fatty acids (for example, dibutoxyethyl succinate and dioctyl acelate), trimesic acid esters (for example, tributyl trimesate) and organic solvents with a boiling point of about 30° to about 150°C, such as alkyl acetates (for example, ethyl acetate and butyl acetate), ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, b-ethoxyethyl acetate or methyl cellosolve acetate. Mixtures of organic solvents can also be used. with a high boiling point and organic solvents with a low boiling point.

It is also possible to use the dispersion method using polymers described in Japanese Patent Publication No. 39853/76 and Japanese Patent Application (OPI) No. 59943/76.

Of the couplers, those having an acidic group, such as a carboxylic acid group or a sulfonic acid group, can be introduced into hydrophilic colloids in the form of an aqueous alkaline solution.

As a binder or protective colloid for the photographic emulsion layers or interlayers of the photographic light-sensitive material of the present invention, gelatin is preferably used, but other hydrophilic colloids may also be used alone or together with gelatin.

As gelatin, not only lime-digested gelatin but also acid-digested gelatin can be used in the present invention. The processes for producing gelatin are described in more detail by Ather Veis, The Macromolecular Chemistry of Gelatin, Academic Press (1964).

As the above-described hydrophilic colloids other than gelatin, it is possible to use proteins such as gelatin derivatives, graft polymers of gelatin and other polymers, albumin and casein; saccharides such as cellulose derivatives such as hydroxyethyl cellulose and cellulose sulfate; sodium alginate and starch derivatives; as well as various synthetic hydrophilic substances of high molecular weight such as homopolymers and copolymers such as polyvinyl alcohol, polyvinyl alcohol semiacetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, Polyvinylimidazole and polyvinylpyrazole.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any of silver halides such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride can be used as the silver halide. A preferred silver halide is silver iodobromide containing 15 mol% or less of silver iodide. A silver iodobromide emulsion containing 2 mol% to 12 mol% of silver iodide is particularly preferred.

Although the average grain size of the silver halide particles in the photographic emulsion is not particularly limited (the average grain size is determined with a grain diameter in the case of particles which are spherical or nearly spherical and an edge length in the case of particles which are cubic as a grain size, and the size is expressed as an average value calculated from the projected areas), it is preferably 6 µm or less.

The grain size distribution can be broad or narrow.

Silver halide particles in the photographic emulsion may have a regular crystal structure such as a cubic or octahedral structure, an irregular crystal structure such as a spherical or plate-like structure, or a composite structure thereof. In addition, silver halide particles composed of those having different crystal structures may be used.

Furthermore, the photographic emulsion can be used in which at least 50% of the total projected area of the silver halide particles is accounted for by tabular silver halide particles having a diameter at least five times their thickness. Especially recommended tabular grain emulsions are those in which more than 50% of the total projected area area of the emulsion grains is made up of tabular grains having a thickness of less than 0.3 µm (0.5 µm in the case of a blue-sensitive emulsion) and having an average tabularity (T) of greater than 25 (preferably greater than 100), the term "tabularity" being used in the manner customary in the art as

T = ECD/t²

wherein

ECD is the mean equivalent circular diameter of the tabular grains in µm (microns) and

t is the average thickness in µm (microns) of the tabular grains.

The inner portion and the surface layer of the silver halide particles may be phase-different. The silver halide particles may be those in which a latent image is mainly formed on the surface or those in which a latent image is mainly formed in the interior of the grains.

The photographic emulsion used in the present invention can be prepared in any suitable manner, for example, by the methods described in the book by P. Glafkides, Chimie et Physique Photographique, Paul Montel (1967), in the book by G.F. Duffin, Photographic Emulsion Chemistry, The Focal Press (1966), and in the book by V.L. Zelikman et al., Making and Coating Photographic Emulsion, The Focal Press (1964). That is, any of acidic methods, neutral methods and ammoniacal methods can be used.

Silver halide emulsions are usually chemically sensitized. For this chemical sensitization, the methods described in the book by H. Frieser, editor, Die Grundlagen der photographischen Prozesse mit Silberhalogeniden, Verlag Akademische Verlagsgesellschaft, pages 675 to 734 (1968) can be used, for example. This means that a sulfur sensitization process can be used using active gelatin or compounds (for example thiosulfates, thioureas, mercapto compounds and rhodanines) containing sulfur that can react with silver; a reduction sensitization process using reducing substances (for example stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid and silane compounds); a precious metal sensitization process using precious metal compounds (for example, complex salts of metals from Group VIII of the Periodic Table of the Elements, such as Pt, Ir and Pd, as well as gold complex salts); or combinations with each other.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fogging or for the purpose of stabilizing the photographic performance in the photographic light-sensitive material during manufacture, storage or photographic processing. For example, there may be incorporated those compounds known as antifoggants or stabilizers, which include azoles such as benzothiazolium salts; nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles and mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; Azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,7)tetraazaindenes) and pentaazaindenes; Benzenethiosulfonic acids; benzenesulfinic acids; and benzenesulfonamides.

In the photographic emulsion layers or other hydrophilic colloid layers of the photographic light-sensitive material of the present invention, various surface active agents may be incorporated as coating assistants or for other various purposes, for example, for preventing charging, improving slip properties, accelerating emulsification and dispersion, preventing adhesion and improving photographic characteristics (for example, improving development acceleration, improving higher contrast and sensitization).

Surfactants that can be used are non-ionic surfactants, for example saponin (steroid-based), alkylene oxide derivatives (for example polyethylene glycol, a polyethylene glycol/polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or polyalkylene glycol alkylamides and silicone/polyethylene oxide adducts), glycidol derivatives (for example alkenylsuccinic acid polyglyceride and alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols and alkyl esters of sugars; anionic surface-active compounds with an acidic group, for example a carboxy group, a sulfo group, a phosphorus group, a sulfuric acid ester group and a phosphoric acid ester group, such as alkylcarboxylic acid salts, alkylsulfonic acid salts, alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, alkylsulfuric acid esters, alkylphosphoric acid esters, N-acyl-N-alkyltaurines, sulfosuccinic acid esters, sulfoalkylpolyoxyethylenealkylphenyl ethers, and polyoxyethylenealkylphosphoric acid esters, amphoteric surface-active agents, such as amino acids, aminoalkylsulfonic acids, aminoalkylsulfuric acid or aminoalkylphosphoric acid esters, alkylbetaines and amine oxides; and cationic surfactants such as alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts (for example pyridinium and imidazolium) and aliphatic or heterocyclic phosphonium or sulfonium salts.

The photographic emulsion layer of the photographic light-sensitive material of the present invention may contain compounds such as polyalkylene oxide or ether, ester or amine derivatives thereof, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives and 3-pyrazolidones for the purpose of increasing the sensitivity or contrast or for the purpose of accelerating the development.

Water-insoluble or slightly soluble dispersions of synthetic polymers may be incorporated into the photographic emulsion layer or other hydrophilic colloid layers of the photographic light-sensitive material of the present invention for the purpose of improving dimensional stability. Synthetic polymers that can be used include homo- or copolymers of alkyl acrylates or methacrylates, alkoxyalkyl acrylates or methacrylates, glycidyl acrylates or methacrylates, acrylamides or methacrylamides, vinyl esters (for example, vinyl acetate), acrylonitrile, olefins and styrene, as well as copolymers of the aforementioned monomers and acrylic acid, methacrylic acid, α,β-unsaturated dicarboxylic acids, hydroxyalkyl acrylates or methacrylates, sulfoalkyl acrylates or methacrylates and styrenesulfonic acid.

The photographic elements can be exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image as described in Research Disclosure, Section XVIII, after which the elements can be processed to form a visible dye image as described in Research Disclosure, Section XIX.

For photographically developing layers composed of photographic emulsions in the photographic light-sensitive material of the present invention, any known method as well as known developing solutions can be used, for example, as described in Research Disclosure, No. 176, pages 28 to 30. The developing temperature is usually selected to be between 18°C and 50°C, although it may be lower than 18°C or higher than 50°C.

Any fixing solutions having compositions that are generally used can be used in the present invention. Thiosulfuric acid salts and thiocyanic acid salts can be used as the fixing agent, and in addition, organic sulfur compounds known to be effective as fixing agents can be used. These fixing solutions can contain water-soluble aluminum salts as hardening agents.

Color developing solutions are generally alkaline aqueous solutions containing color developing agents. As such color developing agents, known developing agents consisting of primary aromatic amines, for example phenylenediamines such as 4-amino-N,N-diethylaniline; 3-methyl-4-amino-N,N-diethylaniline; 4-amino-N-ethyl-N-β-hydroxyethylaniline; 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline; 3-methyl-4-amino-N-β-methanesulfonamidoethylaniline and 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline can be used to prepare exhaustive color reversal developers.

In addition, the compounds described by L.F.A. Mason in Photographic Processing Chemistry, Focal Press, pages 226 to 229 (1966), U.S. Patents 2,193,015 and 2,592,364, and Japanese Patent Application (OPI) 64933/73 can be used.

The color developing solutions may further contain pH buffering agents such as a sulfite, carbonates, borates and phosphates of alkali metals, development inhibitors or antifogging agents such as bromides, iodides and organic antifogging agents. In addition, if desired, the color developing solutions may also contain water softeners, preservatives such as hydroxylamine; organic solvents such as benzyl alcohol and diethylene glycol; development accelerators such as polyethylene glycol, quaternary ammonium salts and amines; dye forming couplers; competitive couplers; fogging agents such as sodium borohydride; auxiliary developing agents; viscosity inducing compounds; acid type chelating agents; and antioxidants.

After color development, the photographic emulsion layer is usually bleached. This bleaching process can be carried out simultaneously with a fixing process, or both process steps can be carried out independently.

Bleaching agents that can be used include compounds of metals such as iron(III), cobalt(III), chromium(VI) and copper(II) compounds. For example, organic complex salts of iron(III) or cobalt(III), for example complex salts of acids (for example nitrilotriacetic acid and 1,3-diamino-2-propanoltetraacetic acid) or of organic acids (for example citric acid, tartaric acid and malonic acid); persulfates; permanganates; and nitrosophenol can be used. Of these compounds, potassium ferricyanide, iron(III) sodium ethylenediaminetetraacetate and iron(III) ammonium ethylenediaminetetraacetate are particularly suitable. Ethylenediaminetetraacetic acid-iron(III) complex salts are suitable both in an independent bleaching solution and in a mono-bath bleach-fixing solution.

The photographic emulsion used in the present invention may also be spectrally sensitized with methine dyes and other dyes. Suitable dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, homopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Of these dyes, cyanine dyes, merocyanine dyes and complex merocyanine dyes are particularly suitable.

The sensitizing dyes may be present in the emulsion together with dyes that do not themselves contribute to enhancing spectral sensitizing effects but provide a supersensitizing effect, or with materials that do not significantly absorb visible light but provide a supersensitizing effect. For example, aminostilbene compounds substituted with a nitrogen-containing heterocyclic group (for example, those described in U.S. Patents 2,933,390 and 3,635,721), aromatic organic acid-formaldehyde condensates (for example, those described in U.S. Patent 3,743,510), cadmium salts, and azaindene compounds may be present.

The present invention is also applicable to a multilayered multicolor photographic material containing layers sensitive to at least two different spectral wavelength ranges arranged on a support. A multilayered color photographic material generally contains at least one red-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer or at least one blue-sensitive silver halide emulsion layer on a support. The arrangement of these layers can be varied if desired. Usually, a coupler providing a cyan dye is present in a red-sensitive emulsion layer. a magenta dye-forming coupler is present in a green-sensitive emulsion layer and a yellow dye-forming coupler is present in a blue-sensitive emulsion layer. However, a different combination may be used if desired.

The color reversal films of this invention are typically multilayer materials as described in U.S. Patent 4,082,553, U.S. Patent 4,729,943, and U.S. Patent 4,912,024, in the section bridging pages 37-38. The support and other elements are well known in the art, for example, see U.S. Patent 4,912,024, column 38, line 37, and the references cited therein. Experimental part Synthesis examples: Synthesis A: Synthes B:

The synthesis of T1 is representative of reactions of inhibitors with compound B4: Synthesis C:

Synthesis example A: Connection Q24

A suspension of monomethyl terephthalate (13.1 g, 72.6 mmol) in dichloromethane (100 mL) was treated with oxalyl chloride (13.5 mL, 152 mmol) followed by the addition of a catalytic amount of DMF (ca. 0.1 g). After stirring for 1.5 h, the volatiles were removed in vacuo to give the acid chloride (A1) as an almost white solid. This was used in the subsequent reaction without further purification.

A solution of the acid chloride A1 (72.6 mmol) in THF (150 mL) was treated with isopropanol (6.1 mL, 79.4 mmol) in the presence of triethylamine (21 mL, 150 mmol) and a catalytic amount of DMAP (ca. 0.1 g) overnight under reflux conditions. After cooling, the solid triethylammonium chloride was removed by filtration. The filtrate was dissolved in ethyl acetate and washed successively with 2 N HCl, water, 5% NaHCO3 and brine, dried (MgSO4) and concentrated in vacuo to give the diester (A2) as a light yellow oil (15.08 g, 94% yield).

Diester A2 (12.43 g, 56 mmol), isopropanol (5 mL), and hydrazine monohydrate (3.44 g, 69 mmol) were combined and sealed in a pressure tube under a nitrogen atmosphere. The tube was heated to 100 °C overnight. Upon cooling, a solid mass formed, which was diluted with alcohol and added to a rapidly stirring ice-water mixture. Hydrazide (A3), a white solid mass, was separated by filtration, washed with water, and dried in vacuo (7.62 g, yield 61%).

A suspension of hydrazide A3 (6.2 g, 27.9 mmol) in isopropanol (80 mL) was treated with aqueous KOH (27.9 mmol in 5 mL water) and carbon disulfide (4.5 mL, 75 mmol), stirred at ambient temperature for 20 min, after which the excess carbon disulfide was distilled off. The resulting mixture was stirred at ambient temperature overnight. The product, Q24, was isolated by pouring the mixture into a rapidly stirred ice-water-HCl mixture to collect the solid, which was washed with water and dried (6.72 g, 91% yield, m.p. 169.5-170.5 °C).

Synthesis example B: Connection B2

3-mercaptopropionic acid (68.6 g, 0.647 mol) and 250 ml water were charged to a 1 L three-neck flask equipped with a reflux condenser with nitrogen gas inlet/outlet, addition funnel, magnetic stirring bar, and thermometer. The solution was cooled to 0ºC. A solution of NaOH (78.0 g, 1.44 mol, 3.1 eq.) in 100 mL of room temperature water was added all at once. The temperature rose to 50ºC. The solution was cooled to room temperature and a solution of 2-chloroethylamine monohydrochloride (75.0 g, 0.647 mol) in 100 mL of water was added over a 10 minute period. The solution was heated to 60ºC for 45 minutes and then cooled to 15ºC. To the vigorously stirred solution of (B1) were added solid NaOH (26.0 g, 0.647 mol) and carbon disulfide (98.4 g, 1.29 mol, 2 eq.). After stirring overnight, the mixture was heated at 45 °C for 15 min. The solution was cooled to 10 °C, the bath was removed and methyl iodide (98.0 g, 0.676 mol) was added. The temperature slowly rose to 20 °C. After 1 h, the solution was heated at 45 °C for 15 min. The solution was cooled to 10 °C, acidified to pH 1 with concentrated HCl and the resulting light green oil was extracted twice with 300 mL of ethyl acetate. The combined extracts were washed twice with 50 mL of 50% brine. The light yellow solution was extracted with 800 mL of 10% NaHCO3 solution and 200 mL of 5% NaHCO3 solution. The combined extracts were acidified with conc. HCl and the resulting oil was extracted with 500 mL and 250 mL of ethyl acetate. The extracts were combined and washed with 100 mL of brine. The solution was dried over MgSO4, filtered and evaporated to give 132 g of (B2) as a light yellow oil. Yield: 85%.

Connection B3

The reaction was carried out in a 1 l flask equipped with a magnetic stir bar and a reflux condenser equipped with a nitrogen inlet/outlet connected via a bubbler to the side arm of a very weakly plugged 4 l Erlenmeyer flask.

The Erlenmeyer flask was filled with 1 gal. of bleach and the bleach was stirred rapidly in an ice bath to act as a methyl mercaptan scrubber. To the flask were added (B2) (130 g, 0.543 mol) and 300 mL of water. The mixture was cooled in an ice bath while 50% NaOH (43.4 g, 0.543 mol) was added portionwise. The pH of the resulting light yellow solution was between 7 and 8. The solution was gently heated to near boiling point under nitrogen with stirring; vigorous evolution of methyl mercaptan began and a small amount of oil was formed. After gentle refluxing for 1 hour, the orange solution was cooled to 40°C and 50 mL of 5% NaHCO3 solution was added. The solution was extracted with 150 mL of ethyl acetate. The aqueous layer was treated with 50 g of NaCl and acidified with 100 mL of conc. HCl; the resulting oil was extracted with 300 mL and 100 mL of ethyl acetate. The ethyl acetate solution was washed with 50 mL of brine and then extracted with 500 mL and 50 mL of 10% NaHCO3 solution. The extracts were combined, acidified with conc. HCl, saturated with NaCl and the resulting oil was extracted with ethyl acetate. The light orange solution was extracted with 50 mL of brine, dried over MgSO4 and dried over 125 mL of ethyl acetate. dried, treated with 5 g of NORIT, filtered and evaporated to a light yellow oil. The oil was triturated with 300 mL of toluene to give (B3) as an almost white waxy solid. The yield was 97.0 g, 76%.

Connection Q21

A solution of (B3) (50.0 g, 0.213 mol), n-butyl alcohol (47 g, 0.639 mol, 3 eq.) and 0.75 ml of conc. sulfuric acid in 75 ml of cyclohexane was heated to reflux for 1 h; the water formed was collected in a Dean-Stark trap filled with 4Å molecular sieves. The solution was cooled and added to 300 ml of ethyl acetate. The solution was extracted twice with 50 ml of water and then with 400 ml and 2 x 50 ml of 5% NaHCO3 solution. The bicarbonate extracts were and acidified with conc. HCl. The resulting oil was extracted with 300 mL and 2 x 50 mL of ethyl acetate. The solution was washed with 50 mL of brine, dried over MgSO4, filtered and evaporated, finally at 80 °C, to give Q21 as a pale yellow oil. Yield: 51 g, 83%.

Connection T1

The synthesis of compound B4 is described in U.S. Patent 5,151,343. Compound B4 (23.7 g, 0.035 mol), Q21 (10.2 g, 0.035 mol), and triethylamine (8.8 g, 0.087 mol, 2.5 eq.) were combined in 100 mL of dry tetrahydrofuran. After 30 minutes, the mixture was poured into 500 mL of ice-water containing 25 mL of conc. HCl. The product was extracted with ethyl acetate and the solution was washed with water, twice with 5% NaHCO3 solution, dilute HCl, water, and brine. The solution was dried over MgSO4, filtered, and evaporated to give a glass. The glass was chromatographed over 1 L of silica gel eluted with a mixture of 7:1 dichloromethane:ethyl acetate to give 26.5 g of a light yellow glass. The glass was crystallized from methanol to give T1, mp 95-97 °C. Yield: 23.1 g, 75%.

Synthesis example C: Connection Q15

Compound C2, 1-(2-carboxyethyl)-5-mercapto-1,2,3,4-tetrazole, was prepared according to the general synthesis procedure described in U.S. Patent 4,782,012. Compound C2 (12.5 g, 71.8 mmol), Compound Cl (8.63 g, 71.8 mmol), 5 mL of N-methylpyrolidinone, and 75 mL of acetonitrile were placed in a 250 mL flask equipped with a magnetic stirrer and a reflux condenser under a nitrogen atmosphere. Solid carbonyldiimidazole (11.5 g, 72.0 mmol). Vigorous gas evolution was observed, followed by the appearance of a precipitate. After stirring for 5 min, 3-thioethyl-2-propanol (C1) (8.63 g, 71.8 mmol) was added and the mixture was heated to reflux for 35 min. The mixture was cooled, the acetonitrile was removed in vacuo and 3N HCl (110 mL) was added to the residue. Extraction of the aqueous mixture was carried out with ethyl acetate (2 x 100 mL). The combined organic layers were washed with water (2 x 100 mL), brine (50 mL), dried (MgSO4), filtered and evaporated to give 18.8 g of (Q15) as a light orange-red oil. Yield: 95%.

All compounds provided satisfactory 300 MHz proton NMR spectra and other analytical data consistent with the desired compounds.

Determination of half-life

The hydrolysis rates of self-decay inhibitors were measured by analyzing the concentration of starting material remaining as a function of time in the reaction solutions. For convenience, the half-lives of the self-decay inhibitors were determined at pH 11.75 and extrapolated to pH 10.0. The reactions were initiated by mixing 0.25 mL of a 0.005 M solution of the self-decay inhibitor (in DMF) with 25.0 mL of a phosphate buffer solution at pH 11.75 (0.010 M total phosphate) to produce an initial self-decay inhibitor concentration of 5.0 x 10-5, a DMF concentration of 1%, and an ionic strength of 0.04. The buffer solution was thermostatted to 38ºC before and after addition of the self-decomposing inhibitor and kept sealed except for transfer of solution by pipette. At various times, 1.0 ml of reaction solution was withdrawn, placed in a 5 ml beaker and quenched with 0.25 ml of 30% acetic acid under vigorous agitation. Stir. The reaction time was taken as the time at which the acetic acid quench solution was added to the reaction solution. The concentration of the self-decay inhibitor was determined by HPLC: SUPELCO C-8 column, using a mobile phase consisting of 28% acetonitrile and 2% acetic acid solution (0.016 M) at a flow rate of 1.0 mL/min. The quantitative measurements (quantitation) were based on peak areas compared to solutions of a self-decay inhibitor of known concentration. The disappearance of self-decay inhibitor occurred according to first order kinetics. A first order rate constant, kobs, was obtained by fitting the concentration versus time data to an exponential decay function. Assuming first order kinetics with respect to hydroxide concentration, the half-life at pH 10.0 would be: t1/2 (10.0) = 101.75 x t1/2 (11.75) = 56[0.693/kobs (11.75)]. The half-lives of the control inhibitors were determined as described above, except for pH 10.0 (carbonate buffer). The data are presented in Table 1 below. Table 1: Table of half-life values

A Procedure for determining the "inhibitor strength" is described below:

First, a green-sensitive silver bromoiodide gelatin emulsion containing 4.0 mole percent iodide and an approximate grain length/thickness ratio of 0.70/0.09 micrometers was mixed with a coupler dispersion containing cyan coupler C-1 dispersed in half its weight of di-n-butyl phthalate. The resulting mixture was coated onto a cellulose triacetate support according to the following format:

The resulting photographic element (hereinafter referred to as the test coating) was cut into 0.305 m (12 inch) x 35 mm strips which were imagewise exposed to light through a test object with graduated density steps in a commercially available Sensitometer (3000 K light source, 0-3 step wedge, with a Wratten 99 filter and a 0.3 ND filter) for 0.01 second to produce a latent developable image. The exposed strip was then cut lengthwise into two 0.305 m (12 inch) x 16 strips. One of the strips thus prepared was subjected to the photographic development sequence given below:

First developer 4 min.

Water wash 2 min.

Reversal bath 2 min.

Color developer 4 min.

Conditioning bath 2 min.

Bleach bath 6 min.

Fixing bath 4 min.

Water wash 2 min.

All solutions of the above procedure were kept at a temperature of 36.9ºC. The compositions of the developing solutions were as follows:

First developer:

Amino-tris(methylenephosphonic acid), pentasodium salt 0.56 g

Diethylenetriaminepentaacetic acid, pentasodium salt 2.50 g

Potassium sulphite 29.75 g

Sodium bromide 2.34 g

Potassium hydroxide 4.28 g

Potassium iodide 4.50 mg

4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone 1.50 g

Potassium carbonate 14.00 g

Sodium bicarbonate 12.00 g

Potassium hydroquinone sulfonate 23.40 g

Acetic acid (glacial acetic acid) 0.58 g

filled with water to 1.0 litre

Reversal bath:

Propionic acid 11.90 g

Stannous chloride (anhydrous) 1.65 g

p-Aminophenol 0.5 mg

Sodium hydroxide 4.96 g

Amino-tris(methylenephosphonic acid), pentasodium salt 8.44 g

filled with water to 1.0 litre

Color developer:

Amino-tris (methylenephosphonic acid), pentasodium salt 2.67 g

Phosphoric acid (75% solution) 17.40 g

Sodium bromide 0.65 g

Potassium iodide 37.5 mg

Potassium hydroxide 27.72 g

Sodium sulphite 6.08 g

Sodium metabisulfite 0.50 g

Citrazinic acid 0.57 g

Methanesulfonamide, N-[2-[(4-amino-3-methyl- phenyl)ethylamino]ethyl]-sulfate (2:3) 10.42 g

3,6-Dithia-1,8-octanediol 0.87 g

Acetic acid (glacial acetic acid) 1.16 g

filled with water to 1.0 litre

Conditioning bath:

(Ethylenedinitrile)tetraacetic acid 8.00 g

Potassium sulphite 13.10 g

Thioglycerin 0.52 g

filled with water to 1.0 litre

Bleach bath:

Potassium nitrate 25.00 g

Ammonium bromide 64.20 g

Ammonium ferri(ethylenediamine) 124.9 g

Hydrobromic acid 24.58 g

(Ethylenedinitrilo)tetraacetic acid 4.00 g

Potassium hydroxide 1.74 g

filled with water to 1.0 litre

Fixing bath:

Ammonium thiosulfate 95.49 g

Ammonium sulphite 6.76 g

(Ethylenedinitrile)tetraacetic acid 0.59 g

Sodium metabisulfite 7.12 g

Sodium hydroxide 1.00 g

filled with water to 1.0 litre

After the test coating was subjected to this development sequence and dried, the maximum density was determined using a commercially available densitometer in the form of Status A densitometry. This density is referred to as Dmax (Solution A). The other half of the exposed test coating was developed by the same development sequence, except that the color developer contained 0.25 mmol of the INH compound in addition to the compounds listed in the formula given above. The inhibitor was dissolved in 1 ml of DMF, added to the color developer and stirred vigorously for 30 seconds before the film strips were immersed for development. The maximum density obtained for this test coating developed in this manner is referred to as Dmax (Solution B). The inhibitor number, IN, of the INH compound is defined as follows:

IN = Dmax (solution A) - Dmax (solution B)/Dmax (solution A) x 100

The inhibitory potency, IS, of the INH compound is defined as follows:

IS = IN (test)/IN (comparison)

where IN (test) is the inhibitor number determined by the method described above for each INH compound of interest and where IN (comparative) is the inhibitor number determined for the test coating when 1-phenyl-5-mercapto-1,2,3,4-tetrazole is the INH compound incorporated into the color developer. Preferably, the development inhibitor has an inhibitor strength of greater than 0.5.

The following examples further illustrate this invention:

Example 1 (comparison)

This example shows that the inhibitors cause inhibition of development at development times, but decompose to inactive species upon standing in the high pH developer and are thus essentially non-seasoning. The comparative examples describe typical prior art hydrolyzable inhibitors and are completely deactivated and ineffective as inhibitors in high pH processes at processing times.

For this study, single layer film strips were prepared by coating and developed for the "inhibitor strength" test as described above. In addition, after standing for one hour, a second film strip was developed through the inhibitor-spiked developer. This procedure was repeated after two hours where appropriate. The inhibitor numbers thus determined are given in Table 2 below. Table 2: Inhibitor numbers

* The time refers to the period of time after the sample was added to the color developer during which single-layer film strips were immersed in the color developer. Example 2

1.0 g of T20 was dissolved in 2.0 g of N,N-diethyllauramide and 3.0 g of ethyl acetate with gentle heating. This solution was then brought to a temperature of 40°C and then mixed with a solution containing 3.0 g of porcine gelatin and 0.3 g of the sodium salt of triisopropylnaphthalenesulfonic acid dissolved in 40.7 g of distilled water. The resulting mixture was then passed through a colloid mill three times to produce a dispersion. This dispersion was then used to prepare a photographic element designated Sample 101 having the composition given below:

In the composition of the layers, the coating amounts are given as g/m², with the exception of the sensitizing dyes, the amounts of which are given in molar amounts per mole of silver halide present in the same layer.

Photographic support: cellulose triacetate with a gelatin subbing layer. First layer: red-sensitive layer Silver iodobromide emulsion (as silver) 1.18

(4 mol% iodide) red-sensitizing dyes 1.42 x 10⊃min;³

Blue-green coupler C-1 1.71

Di-n-butyl phthalate 0.85

T20 0.04

Gelatin 4.03

Second layer: intermediate layer

Competitor S-3 0.16

Dye-1 0.06

Gelatin 0.86

Third layer: green-sensitive layer

Silver iodobromide emulsion (as silver) 1.18

(4 mol% iodide) green sensitizing dyes 2.0 x 10⊃min;³

Coupler M-1 1.67

Tritolyl phosphate 0.84

Gelatin 4.03

Fourth layer: protective layer

Gelatin 3.23

Bis(vinylsulfonylmethane) 0.23 DYE-1 SENSITIZING DYE-1 SENSITIZING DYE-2 Purple absorber dye

Samples 102 to 107 were prepared in a similar manner, except that T20 was replaced with equimolar amounts of the DIR compounds as indicated in Table 3. After drying, the samples were cut into 12 inch x 35 mm strips and exposed as follows:

First, the red-sensitive layer was imagewise exposed to a step wedge with density steps of 0-3 and a Wratten filter 29 using a commercial sensitometer (3000 K lamp temperature) for 0.01 seconds. The green-sensitive layer was then subjected to a uniform flash exposure using the same sensitometer with a Wratten filter 99 but without the step wedge. The intensity of the green exposure was selected to correspond to an exposure that resulted in an analytical Status A green maximum density of approximately 2.0 after photographic development for Sample 100, which was identical in composition to Sample 101, except that it did not contain the DIR compound. The exposed samples were developed using the sequence of development steps described above. All solutions in the process were kept at a temperature of 36.9ºC. The compositions of the developing solutions were the same as described above.

After development, the densities of the samples were read on Status A densitometry using a commercially available densitometer. The densities were converted to analytical densities in the usual manner so that the red and green densities reflected the amounts of cyan and magenta dyes formed in the corresponding layers. The results are summarized in Table 3. It can be seen that the DIR compounds releasing INH-LY residues with inhibitor half-lives greater than 4 hours at pH 10.0 result in greater reductions in maximum red density than the comparative DIR compounds releasing INH-LY residues with inhibitor half-lives less than 4 hours at pH 10.0. The ability to reduce the density in the layer in which the DIR compound is applied is an indication of the ability of the DIR compound to provide sharpness improvements. Also given in Table 3 is a parameter designated Delta Dmax (ΔDmax), which is the difference in the green density measured in an area of the filmstrip where the red density is at a minimum minus the green density measured in an area where the red density is at a maximum. As such, this parameter reflects the ability of a DIR compound applied in one layer to alter the dye formation in another layer. The data in Table 3 show that some DIR compounds, Samples 101 and 102, have a much greater effect on the dye density produced in the green sensitive layer than DIR compounds used for comparison purposes. This very desirable property enables the production of film elements that have fuller color saturation. Table 3

Weak or practically no inhibitory properties mean that the inhibitor does not substantially season the developer after decomposition.

Claims (10)

1. Photographic, light-sensitive silver halide material for development in a developing solution at a pH of at least 11.4, which has a support and a silver halide emulsion layer, characterized in that the silver halide emulsion layer contains a compound which is capable of releasing a development inhibitor with a decay half-life in the range of more than 4 to 225 hours at a pH of 10, the inhibitor having practically no photographic inhibitor properties after decay, the compound corresponding to the formula: CAR-(TIME)n-INH-L-Y (I) where: CAR is a carrier moiety which releases -(TIME)n-INH-L-Y by reaction with oxidized developer; TIME a time control group; INH-L-Y is a development inhibitor moiety in which INH is selected from the group consisting of substituted or unsubstituted oxazole, thiazole, diazole, oxathiazole, triazole, thiatriazole, tetrazole, benzimidazole, indazole, isoindazole, mercaptothiazole, mercaptotriazole, mercaptothiadiazole, mercaptotetrazole, selenotetrazol, mercaptooxadiazole, selenobenzothiazole, mercaptobenzoxazole, selenobenzoxazole, mercaptobenzimidazole, selenobenzimidazole, benzodiazole or benzisodiazole, such that an inhibitor moiety having the group H-INH-L-Y has a calculated log P value of greater than 0.4, and wherein n stands for 0, 1 or 2; L stands for a divalent linking group with a chemical bond that is broken in a photographic developing solution and contains: -CO₂-, -NReCO₂-, -SO₂O-, -OCH₂CH₂SO₂-, -OC(=O)O- or -NReC(=O)C(=O)-, where Re is H, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group; and Y represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. 2. A photographic element according to claim 1 which is a color reversal silver halide photographic light-sensitive material suitable for development by a color reversal process. 3. A photographic element according to claim 1 or 2, wherein the development inhibitor has an inhibitor strength of greater than 0.5. 4. A photographic element according to any one of claims 1 to 3, in which CAR is a coupler moiety. 5. The photographic element of claim 4 wherein CAR is a coupler moiety having a ballast group. 6. A photographic element according to any one of claims 1 to 4, in which CAR does not have a ballast group and at least one of the -(TIME)n residues has a ballast group. 7. A photographic element according to any one of claims 1 to 3, in which CAR is a moiety capable of undergoing cross-oxidation with oxidized color developer and is selected from hydroquinones, catechins, aminophenols, aminonaphthols, sulfonamidophenols, sulfonamidonaphthols and hydrazides. 8. A photographic element according to any preceding claim, wherein the compound is present in the element in an amount of from 0.005 to 0.3 g/m² [0.5 to 30 mg/ft²]. 9. A photographic element according to any preceding claim, wherein the development inhibitor has a decay half-life in the range of 6 to 120 hours at a pH of 10. 10. A process for developing a color reversal photographic element according to any one of claims 2 to 91, which comprises first treating the element with a black and white developer to develop exposed silver halide grains, then fogging unexposed grains and then treating the element with a color developer.